Si PRECURSORS FOR DEPOSITION OF SiN AT LOW TEMPERATURES

ABSTRACT

Methods and precursors for depositing silicon nitride films by atomic layer deposition (ALD) are provided. In some embodiments the silicon precursors comprise an iodine ligand. The silicon nitride films may have a relatively uniform etch rate for both vertical and the horizontal portions when deposited onto three-dimensional structures such as FinFETS or other types of multiple gate FETs. In some embodiments, various silicon nitride films of the present disclosure have an etch rate of less than half the thermal oxide removal rate with diluted HF (0.5%).

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. application Ser. No.16/540,349, filed Aug. 14, 2019, which is a continuation of U.S.application Ser. No. 15/902,300, filed on Feb. 22, 2018, now U.S. Pat.No. 10,395,917, which is a continuation of U.S. application Ser. No.15/414,485, filed on Jan. 24, 2017, now U.S. Pat. No. 9,905,416, whichis a continuation of U.S. application Ser. No. 14/167,904, filed on Jan.29, 2014, now U.S. Pat. No. 9,564,309, which is a continuation-in-partof U.S. application Ser. No. 14/062,328, filed Oct. 24, 2013, which is acontinuation-in-part of U.S. application Ser. No. 13/830,084, filed onMar. 14, 2013, now U.S. Pat. No. 9,824,881, each of which is herebyincorporated by reference in its entirety.

BACKGROUND OF THE INVENTION Field of the Invention

The present disclosure relates generally to the field of semiconductordevice manufacturing and, more particularly, to low temperaturedeposition of silicon nitride films and precursors for use in depositionof silicon nitride films.

Description of the Related Art

Spacers are widely used in semiconductor manufacturing as structures toprotect against subsequent processing steps. For example, nitridespacers formed beside gate electrodes can be used as a mask to protectunderlying source/drain areas during doping or implanting steps.

As the physical geometry of semiconductor devices shrinks, the gateelectrode spacer becomes smaller and smaller. The spacer width islimited by the nitride thickness that can be deposited conformably overthe dense gate electrodes lines. So the nitride spacer etching processis preferred to have a high ratio of spacer width to nitride layerthickness as deposited.

Current PEALD silicon nitride processes in general suffer fromanisotropic etch behavior when deposited on a three-dimensionalstructure, such as a trench structure. In other words, the filmdeposited on the sidewalls of a trench or fin or another threedimensional feature display inferior film properties as compared to filmon the top region of the feature. The film quality may be sufficient forthe target application on the top of the trench, or on planar regions ofa structured wafer, but not on the sidewalls or other nonhorizontal orvertical surfaces.

FIGS. 1A and 1B illustrate a typical example of a silicon nitride film,which could be used in spacer applications. The film was deposited at400° C. using a PEALD process other than those described in the presentapplication. FIG. 1A illustrates the film after it was deposited on athree-dimensional surface but prior to being etched by HF. An etchingprocess was then performed by dipping the workpiece in 0.5% HF for about60 seconds. FIG. 1B illustrates the extent to which vertical portions ofthe silicon nitride film etch to a greater extent than the horizontalportions of the film. The film thicknesses are indicated in nanometers.Structures such as these would not generally survive further processing,such as in a FinFET spacer application.

SUMMARY OF THE INVENTION

In some aspects, atomic layer deposition (ALD) methods of formingsilicon nitride films are provided. The ALD methods may be plasmaenhanced ALD methods or thermal ALD methods. The methods allow for thedeposition of silicon nitride films with desirable qualities, such asgood step coverage and pattern loading effects, as well as desirableetch characteristics. According to some embodiments, the silicon nitridefilms have a relatively uniform etch rate for both the vertical and thehorizontal portions, when deposited onto 3-dimensional structures. Suchthree-dimensional structures may include, for example and withoutlimitation, FinFETS or other types of multiple gate FETs. In someembodiments, various silicon nitride films of the present disclosurehave an etch rate of less than half the thermal oxide removal rate ofabout 2-3 nm per minute with diluted HF (0.5%).

In some embodiments, methods of depositing silicon nitride films onsubstrate in a reaction chamber comprise introducing a vapor phasesilicon reactant to the reaction space such that the silicon precursoradsorbs on the substrate surface, removing excess silicon reactant,contacting the adsorbed silicon reactant with a reactive speciesgenerated by plasma from a nitrogen precursor, and removing excessreactive species and reaction by-products. These steps are repeated toachieve a silicon nitride film of the desired thickness.

In some embodiments, the silicon precursor comprises a precursor offormulas (1)-(8) as described herein. In some embodiments the siliconprecursor is selected from the group consisting of HSiI₃, H₂SiI₂, H₃SiI,H₂Si2I₄, H₄Si2I₂, and H₅Si₂I. In some embodiments the silicon precursoris H₂SiI₂. The reactive species may comprise, for example, hydrogen,hydrogen atoms, hydrogen plasma, hydrogen radicals, N*, NH* or NH₂*radicals.

In some embodiments the silicon nitride film is deposited on athree-dimensional structure. In some embodiments the silicon nitridefilm exhibits a step coverage and pattern loading effect of at leastabout 80%. In some embodiments the structure comprises a sidewall andtop regions and the sidewall wet etch rate (WER) of the silicon nitridefilm relative to the top region WER is less than about 3 in 0.5% dHF. Insome embodiments the etch rate of the silicon nitride film is less thanabout 0.4 nm/min in 0.5% aqueous HF.

In some embodiments, methods of depositing a silicon nitride filmcomprise loading a substrate comprising at least one three-dimensionalfeature into a reaction space, introducing a silicon precursor into thereaction space so that the silicon precursor is adsorbed on a surface ofthe substrate, purging the reaction space of excess silicon precursor,introducing a nitrogen precursor into the reaction space, purging thereaction space of excess nitrogen precursor, and repeating the steps toproduce a film of the desired thickness. In some embodiments the filmhas a step coverage of more than about 50% on the three-dimensionalfeature. In some embodiments the wet etch rate of the silicon nitridefilm is less than about 5 nm/min in 5% aqueous HF. In some embodiments aratio of an etch rate of the silicon nitride film in a sidewall of athree-dimensional structure to an etch rate on a top surface is lessthan about 4. In some embodiments the step coverage is at least about80% or 90%.

In some embodiments, methods of depositing a silicon nitride film on asubstrate comprise, exposing the substrate to a vapor phase siliconprecursor so that the silicon precursor is adsorbed on a surface of thesubstrate, exposing the substrate to a purge gas and/or a vacuum toremove excess precursor and reaction byproducts from the substratesurface, contacting the adsorbed silicon precursor with speciesgenerated by a nitrogen plasma, exposing the substrate to a purge gasand/or a vacuum to remove the species of a nitrogen containing plasmaand reaction byproducts from the substrate surface and from theproximity of the substrate surface, and repeating the steps to produce afilm of the desired thickness.

In some embodiments, methods of depositing a silicon nitride film on asubstrate comprise, exposing the substrate to a vapor phase siliconreactant so that the silicon reactant is adsorbed on a surface of thesubstrate, exposing the substrate to a purge gas and/or a vacuum toremove excess precursor and reaction byproducts from the substratesurface, contacting the adsorbed silicon reactant with a nitrogenprecursor, exposing the substrate to a purge gas and/or a vacuum toremove excess nitrogen precursor and reaction byproducts from thesubstrate surface and from the proximity of the substrate surface, andrepeating the steps to produce a film of the desired thickness.

In some embodiments the silicon precursor comprises iodine or bromine.In some embodiments the film has a step coverage of more than about 50%.In some embodiments the etch rate of the silicon nitride is less thanabout 5 nm/min in 0.5% aqueous HF. In some embodiments a ratio of anetch rate of the silicon nitride on a sidewall of a three-dimensionalstructure to an etch rate on a top surface of the three-dimensionalstructure is less than about 4.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be better understood from the Detailed Description ofthe Preferred Embodiments and from the appended drawings, which aremeant to illustrate and not to limit the invention, and wherein:

FIGS. 1A and 1B illustrate the results of an etching process on asilicon nitride film;

FIG. 2 is a flow chart generally illustrating a method of forming asilicon nitride film by an ALD process in accordance with someembodiments of the present disclosure;

FIG. 3 is a flow chart illustrating a method of forming a siliconnitride thin film by a PEALD process in accordance with some embodimentsof the present disclosure;

FIG. 4 is a flow chart illustrating a method of forming a siliconnitride thin film by a thermal ALD process in accordance with someembodiments of the present disclosure;

FIGS. 5A-5C illustrate field emission scanning electron microscopy(FESEM) images of various silicon nitride films deposited according tosome embodiments of the present disclosure.

FIGS. 6A-6C illustrate FESEM images of the silicon nitride films ofFIGS. 5A-5B after exposure to a 2-minute dHF dip.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Silicon nitride films have a wide variety of applications, as will beapparent to the skilled artisan, such as in planar logic, DRAM, and NANDFlash devices. More specifically, conformal silicon nitride thin filmsthat display uniform etch behavior have a wide variety of applications,both in the semiconductor industry and also outside of the semiconductorindustry. According to some embodiments of the present disclosure,various silicon nitride films and precursors and methods for depositingthose films by atomic layer deposition (ALD) are provided. Importantly,in some embodiments the silicon nitride films have a relatively uniformetch rate for both the vertical and the horizontal portions, whendeposited onto 3-dimensional structures. Such three-dimensionalstructures may include, for example and without limitation, FinFETS orother types of multiple gate FETs. In some embodiments, various siliconnitride films of the present disclosure have an etch rate of less thanhalf the thermal oxide removal rate of about 2-3 nm per minute withdiluted HF (0.5%).

Thin film layers comprising silicon nitride can be deposited byplasma-enhanced atomic layer deposition (PEALD) type processes or bythermal ALD processes. In some embodiments, silicon nitride thin filmsare deposited on a substrate by PEALD. In some embodiments, siliconnitride thin films are deposited on a substrate by a thermal ALDprocess. In some embodiments a silicon nitride thin film is depositedover a three dimensional structure, such as a fin in the formation of afinFET device.

The formula of the silicon nitride is generally referred to herein asSiN for convenience and simplicity. However, the skilled artisan willunderstand that the actual formula of the silicon nitride, representingthe Si:N ratio in the film and excluding hydrogen or other impurities,can be represented as SiN_(x), where x varies from about 0.5 to about2.0, as long as some Si—N bonds are formed. In some cases, x may varyfrom about 0.9 to about 1.7, from about 1.0 to about 1.5, or from about1.2 to about 1.4. In some embodiments silicon nitride is formed where Sihas an oxidation state of +IV and the amount of nitride in the materialmight vary.

ALD-type processes are based on controlled, generally self-limitingsurface reactions. Gas phase reactions are typically avoided bycontacting the substrate alternately and sequentially with thereactants. Vapor phase reactants are separated from each other in thereaction chamber, for example, by removing excess reactants and/orreactant byproducts between reactant pulses. The reactants may beremoved from proximity with the substrate surface with the aid of apurge gas and/or vacuum. In some embodiments excess reactants and/orreactant byproducts are removed from the reaction space by purging, forexample with an inert gas.

The methods presented herein provide for deposition of SiN thin films onsubstrate surfaces. Geometrically challenging applications are alsopossible due to the nature of ALD-type processes. According to someembodiments, ALD-type processes are used to form SiN thin films onsubstrates such as integrated circuit workpieces, and in someembodiments on three-dimensional structures on the substrates.

FIG. 2 is a flow chart generally illustrating a silicon nitride ALDdeposition cycle that can be used to deposit a silicon nitride thin filmin accordance with some embodiments. According to certain embodiments, asilicon nitride thin film is formed on a substrate by an ALD-typeprocess comprising multiple silicon nitride deposition cycles, eachsilicon nitride deposition cycle 200 comprising:

(1) contacting a substrate with a silicon precursor 210 such that thesilicon precursor adsorbs on the substrate surface;

(2) contacting the substrate with a nitrogen precursor 220; and

(3) repeating steps 210 and 220 as many times as required to achieve athin film of a desired thickness and composition.

Excess reactants may be removed from the vicinity of the substrate, forexample by purging from the reaction space with an inert gas, after eachcontacting step. The discussion below addresses each of these steps ingreater detail.

PEALD Processes

In some embodiments, plasma enhanced ALD (PEALD) processes are used todeposit SiN films. Briefly, a substrate or workpiece is placed in areaction chamber and subjected to alternately repeated surfacereactions. In some embodiments, thin SiN films are formed by repetitionof a self-limiting ALD cycle. Preferably, for forming SiN films, eachALD cycle comprises at least two distinct phases. The provision andremoval of a reactant from the reaction space may be considered a phase.In a first phase, a first reactant comprising silicon is provided andforms no more than about one monolayer on the substrate surface. Thisreactant is also referred to herein as “the silicon precursor,”“silicon-containing precursor,” or “silicon reactant” and may be, forexample, H₂SiI₂.

In a second phase, a second reactant comprising a reactive species isprovided and may convert adsorbed silicon to silicon nitride. In someembodiments the second reactant comprises a nitrogen precursor. In someembodiments, the reactive species comprises an excited species. In someembodiments the second reactant comprises a species from a nitrogencontaining plasma. In some embodiments, the second reactant comprisesnitrogen radicals, nitrogen atoms and/or nitrogen plasma. The secondreactant may comprise other species that are not nitrogen precursors. Insome embodiments, the second reactant may comprise a plasma of hydrogen,radicals of hydrogen, or atomic hydrogen in one form or another. In someembodiments, the second reactant may comprise a species from a noblegas, such as He, Ne, Ar, Kr, or Xe, preferably Ar or He, for example asradicals, in plasma form, or in elemental form. These reactive speciesfrom noble gases do not necessarily contribute material to the depositedfilm, but can in some circumstances contribute to film growth as well ashelp in the formation and ignition of plasma. In some embodiments a gasthat is used to form a plasma may flow constantly throughout thedeposition process but only be activated intermittently. In someembodiments, the second reactant does not comprise a species from anoble gas, such as Ar. Thus, in some embodiments the adsorbed siliconprecursor is not contacted with a reactive species generated by a plasmafrom Ar

Additional phases may be added and phases may be removed as desired toadjust the composition of the final film.

One or more of the reactants may be provided with the aid of a carriergas, such as Ar or He. In some embodiments the silicon precursor and thesecond reactant are provided with the aid of a carrier gas.

In some embodiments, two of the phases may overlap, or be combined. Forexample, the silicon precursor and the second reactant may be providedsimultaneously in pulses that partially or completely overlap. Inaddition, although referred to as the first and second phases, and thefirst and second reactants, the order of the phases may be varied, andan ALD cycle may begin with any one of the phases. That is, unlessspecified otherwise, the reactants can be provided in any order, and theprocess may begin with any of the reactants.

As discussed in more detail below, in some embodiments for depositing asilicon nitride film, one or more deposition cycles begin with provisionof the silicon precursor, followed by the second precursor. In otherembodiments deposition may begin with provision of the second precursor,followed by the silicon precursor.

In some embodiments the substrate on which deposition is desired, suchas a semiconductor workpiece, is loaded into a reactor. The reactor maybe part of a cluster tool in which a variety of different processes inthe formation of an integrated circuit are carried out. In someembodiments a flow-type reactor is utilized. In some embodiments ashower head type of reactor is utilized. In some embodiments, a spacedivided reactor is utilized. In some embodiments a high-volumemanufacturing-capable single wafer ALD reactor is used. In otherembodiments a batch reactor comprising multiple substrates is used. Forembodiments in which batch ALD reactors are used, the number ofsubstrates is preferably in the range of 10 to 200, more preferably inthe range of 50 to 150, and most preferably in the range of 100 to 130.

Exemplary single wafer reactors, designed specifically to enhance ALDprocesses, are commercially available from ASM America, Inc. (Phoenix,Ariz.) under the tradenames Pulsar® 2000 and Pulsar® 3000 and ASM JapanK.K (Tokyo, Japan) under the tradename Eagle® XP, XP8 and Dragon®.Exemplary batch ALD reactors, designed specifically to enhance ALDprocesses, are commercially available from and ASM Europe B.V (Almere,Netherlands) under the tradenames A400™ and A412™.

In some embodiments, if necessary, the exposed surfaces of the workpiececan be pretreated to provide reactive sites to react with the firstphase of the ALD process. In some embodiments a separate pretreatmentstep is not required. In some embodiments the substrate is pretreated toprovide a desired surface termination. In some embodiments the substrateis pretreated with plasma.

Excess reactant and reaction byproducts, if any, are removed from thevicinity of the substrate, and in particular from the substrate surface,between reactant pulses. In some embodiments the reaction chamber ispurged between reactant pulses, such as by purging with an inert gas.The flow rate and time of each reactant, is tunable, as is the removalstep, allowing for control of the quality and various properties of thefilms.

As mentioned above, in some embodiments a gas is provided to thereaction chamber continuously during each deposition cycle, or duringthe entire ALD process, and reactive species are provided by generatinga plasma in the gas, either in the reaction chamber or upstream of thereaction chamber. In some embodiments the gas comprises nitrogen. Insome embodiments the gas is nitrogen. In other embodiments the gas maycomprise helium, or argon. In some embodiments the gas is helium ornitrogen. The flowing gas may also serve as a purge gas for the firstand/or second reactant (or reactive species). For example, flowingnitrogen may serve as a purge gas for a first silicon precursor and alsoserve as a second reactant (as a source of reactive species). In someembodiments, nitrogen, argon, or helium may serve as a purge gas for afirst precursor and a source of excited species for converting thesilicon precursor to the silicon nitride film. In some embodiments thegas in which the plasma is generated does not comprise argon and theadsorbed silicon precursor is not contacted with a reactive speciesgenerated by a plasma from Ar.

The cycle is repeated until a film of the desired thickness andcomposition is obtained. In some embodiments the deposition parameters,such as the flow rate, flow time, purge time, and/or reactantsthemselves, may be varied in one or more deposition cycles during theALD process in order to obtain a film with the desired characteristics.In some embodiments, hydrogen and/or hydrogen plasma are not provided ina deposition cycle, or in the deposition process.

The term “pulse” may be understood to comprise feeding reactant into thereaction chamber for a predetermined amount of time. The term “pulse”does not restrict the length or duration of the pulse and a pulse can beany length of time.

In some embodiments, the silicon reactant is provided first. After aninitial surface termination, if necessary or desired, a first siliconreactant pulse is supplied to the workpiece. In accordance with someembodiments, the first reactant pulse comprises a carrier gas flow and avolatile silicon species, such as H₂SiI₂, that is reactive with theworkpiece surfaces of interest. Accordingly, the silicon reactantadsorbs upon these workpiece surfaces. The first reactant pulseself-saturates the workpiece surfaces such that any excess constituentsof the first reactant pulse do not further react with the molecularlayer formed by this process.

The first silicon reactant pulse is preferably supplied in gaseous form.The silicon precursor gas is considered “volatile” for purposes of thepresent description if the species exhibits sufficient vapor pressureunder the process conditions to transport the species to the workpiecein sufficient concentration to saturate exposed surfaces.

In some embodiments the silicon reactant pulse is from about 0.05seconds to about 5.0 seconds, about 0.1 seconds to about 3 seconds orabout 0.2 seconds to about 1.0 seconds. The optimum pulsing time can bereadily determined by the skilled artisan based on the particularcircumstances.

In some embodiments the silicon reactant consumption rate is selected toprovide a desired dose of precursor to the reaction space. Reactantconsumption refers to the amount of reactant consumed from the reactantsource, such as a reactant source bottle, and can be determined byweighing the reactant source before and after a certain number ofdeposition cycles and dividing the mass difference by the number ofcycles. In some embodiments the silicon reactant consumption is morethan about 0.1 mg/cycle. In some embodiments the silicon reactantconsumption is about 0.1 mg/cycle to about 50 mg/cycle, about 0.5mg/cycle to about 30 mg/cycle or about 2 mg/cycle to about 20 mg/cycle.In some embodiments the minimum preferred silicon reactant consumptionmay be at least partly defined by the reactor dimensions, such as theheated surface area of the reactor. In some embodiments in a showerheadreactor designed for 300 mm silicon wafers, silicon reactant consumptionis more than about 0.5 mg/cycle, or more than about 2.0 mg/cycle. Insome embodiments the silicon reactant consumption is more than about 5mg/cycle in a showerhead reactor designed for 300 mm silicon wafers. Insome embodiments the silicon reactant consumption is more than about 1mg/cycle, preferably more than 5 mg/cycle at reaction temperatures belowabout 400° C. in a showerhead reactor designed for 300 mm siliconwafers.

After sufficient time for a molecular layer to adsorb on the substratesurface, excess first silicon reactant is then removed from the reactionspace. In some embodiments the excess first reactant is purged bystopping the flow of the first chemistry while continuing to flow acarrier gas or purge gas for a sufficient time to diffuse or purgeexcess reactants and reactant by-products, if any, from the reactionspace. In some embodiments the excess first precursor is purged with theaid of inert gas, such as nitrogen or argon, that is flowing throughoutthe ALD cycle.

In some embodiments, the first reactant is purged for about 0.1 secondsto about 10 seconds, about 0.3 seconds to about 5 seconds or about 0.3seconds to about 1 second. Provision and removal of the silicon reactantcan be considered the first or silicon phase of the ALD cycle.

In the second phase, a second reactant comprising a reactive species,such as nitrogen plasma is provided to the workpiece. Nitrogen, N₂, isflowed continuously to the reaction chamber during each ALD cycle insome embodiments. Nitrogen plasma may be formed by generating a plasmain nitrogen in the reaction chamber or upstream of the reaction chamber,for example by flowing the nitrogen through a remote plasma generator.

In some embodiments, plasma is generated in flowing H₂ and N₂ gases. Insome embodiments the H₂ and N₂ are provided to the reaction chamberbefore the plasma is ignited or nitrogen and hydrogen atoms or radicalsare formed. Without being bound to any theory, it is believed that thehydrogen may have a beneficial effect on the ligand removal step i.e. itmay remove some of the remaining ligands or have other beneficialeffects on the film quality. In some embodiments the H₂ and N₂ areprovided to the reaction chamber continuously and nitrogen and hydrogencontaining plasma, atoms or radicals is created or supplied when needed.

Typically, the second reactant, for example comprising nitrogen plasma,is provided for about 0.1 seconds to about 10 seconds. In someembodiments the second reactant, such as nitrogen plasma, is providedfor about 0.1 seconds to about 10 seconds, 0.5 seconds to about 5seconds or 0.5 seconds to about 2.0 seconds. However, depending on thereactor type, substrate type and its surface area, the second reactantpulsing time may be even higher than about 10 seconds. In someembodiments, pulsing times can be on the order of minutes. The optimumpulsing time can be readily determined by the skilled artisan based onthe particular circumstances.

In some embodiments the second reactant is provided in two or moredistinct pulses, without introducing another reactant in between any ofthe two or more pulses. For example, in some embodiments a nitrogenplasma is provided in two or more, preferably in two, sequential pulses,without introducing a Si-precursor in between the sequential pulses. Insome embodiments during provision of nitrogen plasma two or moresequential plasma pulses are generated by providing a plasma dischargefor a first period of time, extinguishing the plasma discharge for asecond period of time, for example from about 0.1 seconds to about 10seconds, from about 0.5 seconds to about 5 seconds or about 1.0 secondsto about 4.0 seconds, and exciting it again for a third period of timebefore introduction of another precursor or a removal step, such asbefore the Si-precursor or a purge step. Additional pulses of plasma canbe introduced in the same way. In some embodiments a plasma is ignitedfor an equivalent period of time in each of the pulses.

Nitrogen plasma may be generated by applying RF power of from about 10Wto about 2000 W, preferably from about 50 W to about 1000 W, morepreferably from about 100 W to about 500 W in some embodiments. In someembodiments the RF power density may be from about 0.02 W/cm² to about2.0 W/cm², preferably from about 0.05 W/cm2 to about 1.5 W/cm2. The RFpower may be applied to nitrogen that flows during the nitrogen plasmapulse time, that flows continuously through the reaction chamber, and/orthat flows through a remote plasma generator. Thus in some embodimentsthe plasma is generated in situ, while in other embodiments the plasmais generated remotely. In some embodiments a showerhead reactor isutilized and plasma is generated between a susceptor (on top of whichthe substrate is located) and a showerhead plate. In some embodimentsthe gap between the susceptor and showerhead plate is from about 0.1 cmto about 20 cm, from about 0.5 cm to about 5 cm, or from about 0.8 cm toabout 3.0 cm.

After a time period sufficient to completely saturate and react thepreviously adsorbed molecular layer with the nitrogen plasma pulse, anyexcess reactant and reaction byproducts are removed from the reactionspace. As with the removal of the first reactant, this step may comprisestopping the generation of reactive species and continuing to flow theinert gas, such as nitrogen or argon for a time period sufficient forexcess reactive species and volatile reaction by-products to diffuse outof and be purged from the reaction space. In other embodiments aseparate purge gas may be used. The purge may, in some embodiments, befrom about 0.1 seconds to about 10 seconds, about 0.1 seconds to about 4seconds or about 0.1 seconds to about 0.5 seconds. Together, thenitrogen plasma provision and removal represent a second, reactivespecies phase in a silicon nitride atomic layer deposition cycle.

The two phases together represent one ALD cycle, which is repeated toform silicon nitride thin films of a desired thickness. While the ALDcycle is generally referred to herein as beginning with the siliconphase, it is contemplated that in other embodiments the cycle may beginwith the reactive species phase. One of skill in the art will recognizethat the first precursor phase generally reacts with the terminationleft by the last phase in the previous cycle. Thus, while no reactantmay be previously adsorbed on the substrate surface or present in thereaction space if the reactive species phase is the first phase in thefirst ALD cycle, in subsequent cycles the reactive species phase willeffectively follow the silicon phase. In some embodiments one or moredifferent ALD cycles are provided in the deposition process.

According to some embodiments of the present disclosure, PEALD reactionsmay be performed at temperatures ranging from about 25° C. to about 700°C., preferably from about 50° C. to about 600° C., more preferably fromabout 100° C. to about 450° C., and most preferably from about 200° C.to about 400° C. In some embodiments, the optimum reactor temperaturemay be limited by the maximum allowed thermal budget. Therefore, in someembodiments the reaction temperature is from about 300° C. to about 400°C. In some applications, the maximum temperature is around about 400°C., and, therefore the PEALD process is run at that reactiontemperature.

According to some embodiments of the present disclosure, the pressure ofthe reaction chamber during processing is maintained at from about 0.01torr to about 50 torr, preferably from about 0.1 torr to about 10 torr.

Si Precursors

A number of suitable silicon precursors can be used in the presentlydisclosed PEALD processes. At least some of the suitable precursors mayhave the following general formula:

H_(2n+2−y−z)Si_(n)X_(y)A_(z)  (1)

-   -   wherein, n=1-10, y=1 or more (and up to 2n+2−z), z=0 or more        (and up to 2n+2−y), X is I or Br, and A is a halogen other than        X, preferably n=1-5 and more preferably n=1-3 and most        preferably 1-2.

According to some embodiments, silicon precursors may comprise one ormore cyclic compounds. Such precursors may have the following generalformula:

H_(2n−y−z)Si_(n)X_(y)A_(z)  (2)

-   -   wherein the formula (2) compound is cyclic compound, n=3-10, y=1        or more (and up to 2n−z), z=0 or more (and up to 2n−y), X is I        or Br, and A is a halogen other than X, preferably n=3-6.

According to some embodiments, silicon precursors may comprise one ormore iodosilanes. Such precursors may have the following generalformula:

H_(2n+2−y−z)Si_(n)I_(y)A_(z)  (3)

-   -   wherein, n=1-10, y=1 or more (and up to 2n+2−z), z=0 or more        (and up to 2n+2−y), and A is a halogen other than I, preferably        n=1-5 and more preferably n=1-3 and most preferably 1-2.

According to some embodiments, some silicon precursors may comprise oneor more cyclic iodosilanes. Such precursors may have the followinggeneral formula:

H_(2n−y−z)Si_(n)I_(y)A_(z)  (4)

-   -   wherein the formula (4) compound is a cyclic compound, n=3-10,        y=1 or more (and up to 2n−z), z=0 or more (and up to 2n−y), and        A is a halogen other than I, preferably n=3-6.

According to some embodiments, some silicon precursors may comprise oneor more bromosilanes. Such precursors may have the following generalformula:

H_(2n+2−y−z)Si_(n)Br_(y)A_(z)  (5)

-   -   wherein, n=1-10, y=1 or more (and up to 2n+2−z), z=0 or more        (and up to 2n+2−y), and A is a halogen other than Br, preferably        n=1-5 and more preferably n=1-3 and most preferably 1-2.

According to some embodiments, some silicon precursors may comprise oneor more cyclic bromosilanes. Such precursors may have the followinggeneral formula:

H_(2n−y−z)Si_(n)Br_(y)A_(z)  (6)

-   -   wherein the formula (6) compound is a cyclic compound, n=3-10,        y=1 or more (and up to 2n−z), z=0 or more (and up to 2n−y), and        A is a halogen other than Br, preferably n=3-6.

According to some embodiments, preferred silicon precursors comprise oneor more iodosilanes. Such precursors may have the following generalformula:

H_(2n+2−y)Si_(n)I_(y)  (7)

-   -   wherein, n=1-5, y=1 or more (up to 2n+2), preferably n=1-3 and        more preferably n=1-2.

According to some embodiments, preferred silicon precursors comprise oneor more bromosilanes. Such precursors may have the following generalformula:

H_(2n+2−y)Si_(n)Br_(y)  (8)

-   -   wherein, n=1-5, y=1 or more (up to 2n+2), preferably n=1-3 and        more preferably n=1-2.

According to some embodiments of a PEALD process, suitable siliconprecursors can include at least compounds having any one of the generalformulas (1) through (8). In general formulas (1) through (8),halides/halogens can include F, Cl, Br and I. In some embodiments, asilicon precursor comprises SiI₄, HSiI₃, H₂SiI₂, H₃SiI, Si₂I₆, HSi₂I₅,H₂SiI₂I₄, H₃Si₂I₃, H₄Si₂I₂, H₅Si₃I, or Si₃I₈. In some embodiments, asilicon precursor comprises one of HSiI₃, H₂SiI₂, H₃SiI, H₂SiI₂I₄,H₄Si₂I₂, and H₅Si₂I. In some embodiments the silicon precursor comprisestwo, three, four, five or six of HSiI₃, H₂SiI₂, H₃SiI, H₂Si₂I₄, H₄Si₂I₂,and H₅Si₂I, including any combinations thereof.

In certain embodiments, the Si precursor is H₂SiI₂.

In some embodiments, Si precursors of formulas (9)-(28), below, can beused in PEALD processes.

N Precursors

As discussed above, the second reactant in a PEALD process according tothe present disclosure may comprise a nitrogen precursor, which maycomprise a reactive species. Suitable plasma compositions includenitrogen plasma, radicals of nitrogen, or atomic nitrogen in one form oranother. In some embodiments, hydrogen plasma, radicals of hydrogen, oratomic hydrogen in one form or another are also provided. And in someembodiments, a plasma may also contain noble gases, such as He, Ne, Ar,Kr and Xe, preferably Ar or He, in plasma form, as radicals, or inatomic form. In some embodiments, the second reactant does not compriseany species from a noble gas, such as Ar. Thus, in some embodimentsplasma is not generated in a gas comprising a noble gas.

Thus, in some embodiments the second reactant may comprise plasma formedfrom compounds having both N and H, such as NH₃ and N₂H₄, a mixture ofN₂/H₂ or other precursors having an N—H bond. In some embodiments thesecond reactant may be formed, at least in part, from N₂. In someembodiments the second reactant may be formed, at least in part, from N₂and H₂, where the N₂ and H₂ are provided at a flow ratio (N₂/H₂) fromabout 20:1 to about 1:20, preferably from about 10:1 to about 1:10, morepreferably from about 5:1 to about 1:5 and most preferably from about1:2 to about 4:1, and in some cases 1:1.

The second reactant may be formed in some embodiments remotely viaplasma discharge (“remote plasma”) away from the substrate or reactionspace. In some embodiments, the second reactant may be formed in thevicinity of the substrate or directly above substrate (“direct plasma”).

FIG. 3 is a flow chart generally illustrating a silicon nitride PEALDdeposition cycle that can be used to deposit a silicon nitride thin filmin accordance with some embodiments. According to certain embodiment, asilicon nitride thin film is formed on a substrate by a PEALD-typeprocess comprising multiple silicon nitride deposition cycles, eachsilicon nitride deposition cycle 300 comprising:

(1) contacting a substrate with a vaporized silicon precursor 310 suchthat the silicon compound adsorbs on the substrate surface;

(2) introduction of a nitrogen precursor into a reaction space 320;

(3) generating a reactive species from a nitrogen precursor 330; and

(4) contacting the substrate with the reactive species 340, therebyconverting the adsorbed silicon compound into silicon nitride.

Nitrogen may flow continuously throughout the cycle, with nitrogenplasma formed at the appropriate times to convert adsorbed siliconcompound into silicon nitride.

As mentioned above, in some embodiments the substrate may be contactedsimultaneously with the silicon compound and the reactive species, whilein other embodiments these reactants are provided separately.

The contacting steps are repeated 350 until a thin film of a desiredthickness and composition is obtained. Excess reactants may be purgedfrom the reaction space after each contacting step, i.e., steps 310 and340.

According to some embodiments, a silicon nitride thin film is depositedusing a PEALD process on a substrate having three-dimensional features,such as in a FinFET application. The process may comprise the followingsteps:

(1) a substrate comprising a three-dimensional structure is provided ina reaction space;

(2) a silicon-containing precursor, such as SiI₂H₂, is introduced intothe reaction space so that the silicon-containing precursor is adsorbedto a surface of the substrate;

(3) excess silicon-containing precursor and reaction byproducts areremoved from the reaction space;

(4) a nitrogen-containing precursor, such as N₂, NH₃, N₂H₄, or N₂ andH₂, is introduced into the reaction space;

(5) generating reactive species from the nitrogen precursor;

(6) contacting the substrate with the reactive species; and

(7) removing excess nitrogen atoms, plasma, or radicals and reactionbyproducts;

Steps (2) through (7) may be repeated until a silicon nitride film of adesired thickness is formed.

In some embodiments steps (5) and (6) are replaced by a step in whichthe nitrogen atoms, plasma or radicals are formed remotely and providedto the reaction space.

In some embodiments, the PEALD process is performed at a temperaturebetween about 200° C. to about 400° C., between about 300° C. and about400° C., or at about 400° C.

Thermal ALD Processes

The methods presented herein also allow deposition of silicon nitridefilms on substrate surfaces by thermal ALD processes. Geometricallychallenging applications, such as 3-dimensional structures, are alsopossible with these thermal processes. According to some embodiments,thermal atomic layer deposition (ALD) type processes are used to formsilicon nitride films on substrates such as integrated circuitworkpieces.

A substrate or workpiece is placed in a reaction chamber and subjectedto alternately repeated, self-limiting surface reactions. Preferably,for forming silicon nitride films each thermal ALD cycle comprises atleast two distinct phases. The provision and removal of a reactant fromthe reaction space may be considered a phase. In a first phase, a firstreactant comprising silicon is provided and forms no more than about onemonolayer on the substrate surface. This reactant is also referred toherein as “the silicon precursor” or “silicon reactant” and may be, forexample, H2SiI2. In a second phase, a second reactant comprising anitrogen-containing compound is provided and reacts with the adsorbedsilicon precursor to form SiN. This second reactant may also be referredto as a “nitrogen precursor” or “nitrogen reactant.” The second reactantmay comprise NH₃ or another suitable nitrogen-containing compound.Additional phases may be added and phases may be removed as desired toadjust the composition of the final film.

One or more of the reactants may be provided with the aid of a carriergas, such as Ar or He. In some embodiments the silicon precursor and thenitrogen precursor are provided with the aid of a carrier gas.

In some embodiments, two of the phases may overlap, or be combined. Forexample, the silicon precursor and the nitrogen precursor may beprovided simultaneously in pulses that partially or completely overlap.In addition, although referred to as the first and second phases, andthe first and second reactants, the order of the phases and the order ofprovision of reactants may be varied, and an ALD cycle may begin withany one of the phases or any of the reactants. That is, unless specifiedotherwise, the reactants can be provided in any order and the processmay begin with any of the reactants.

As discussed in more detail below, in some embodiments for depositing asilicon nitride film, one or more deposition cycles typically beginswith provision of the silicon precursor followed by the nitrogenprecursor. In some embodiments, one or more deposition cycles beginswith provision of the nitrogen precursor followed by the siliconprecursor.

Again, one or more of the reactants may be provided with the aid of acarrier gas, such as Ar or He. In some embodiments the nitrogenprecursor is provided with the aid of a carrier gas. In someembodiments, although referred to as a first phase and a second phaseand a first and second reactant, the order of the phases and thus theorder of provision of the reactants may be varied, and an ALD cycle maybegin with any one of the phases.

In some embodiments the substrate on which deposition is desired, suchas a semiconductor workpiece, is loaded into a reactor. The reactor maybe part of a cluster tool in which a variety of different processes inthe formation of an integrated circuit are carried out. In someembodiments a flow-type reactor is utilized. In some embodiments ashower head type of reactor is utilized. In some embodiments a spacedivided reactor is utilized. In some embodiments a high-volumemanufacturing-capable single wafer ALD reactor is used. In otherembodiments a batch reactor comprising multiple substrates is used. Forembodiments in which batch ALD reactors are used, the number ofsubstrates is preferably in the range of 10 to 200, more preferably inthe range of 50 to 150, and most preferably in the range of 100 to 130.

Exemplary single wafer reactors, designed specifically to enhance ALDprocesses, are commercially available from ASM America, Inc. (Phoenix,Ariz.) under the tradenames Pulsar® 2000 and Pulsar® 3000 and ASM JapanK.K (Tokyo, Japan) under the tradename Eagle® XP, XP8 and Dragon®.Exemplary batch ALD reactors, designed specifically to enhance ALDprocesses, are commercially available from and ASM Europe B.V (Almere,Netherlands) under the tradenames A400™ and A412™.

In some embodiments, if necessary, the exposed surfaces of the workpiececan be pretreated to provide reactive sites to react with the firstphase of the ALD process. In some embodiments a separate pretreatmentstep is not required. In some embodiments the substrate is pretreated toprovide a desired surface termination.

In some embodiments, excess reactant and reaction byproducts, if any,are removed from the vicinity of the precursor, such as from thesubstrate surface, between reactant pulses. In some embodiments excessreactant and reaction byproducts are removed from the reaction chamberby purging between reactant pulses, for example with an inert gas. Theflow rate and time of each reactant, is tunable, as is the purge step,allowing for control of the quality and properties of the films. In someembodiments removing excess reactant and/or reaction byproductscomprises moving the substrate.

As mentioned above, in some embodiments, a gas is provided to thereaction chamber continuously during each deposition cycle, or duringthe entire ALD process. In other embodiments the gas may be nitrogen,helium or argon.

The ALD cycle is repeated until a film of the desired thickness andcomposition is obtained. In some embodiments the deposition parameters,such as the flow rate, flow time, purge time, and/or precursorsthemselves, may be varied in one or more deposition cycles during theALD process in order to obtain a film with the desired characteristics.

The term “pulse” may be understood to comprise feeding reactant into thereaction chamber for a predetermined amount of time. The term “pulse”does not restrict the length or duration of the pulse and a pulse can beany length of time.

In some embodiments, the silicon precursor is provided first. After aninitial surface termination, if necessary or desired, a first siliconprecursor pulse is supplied to the workpiece. In accordance with someembodiments, the first precursor pulse comprises a carrier gas flow anda volatile silicon species, such as H₂SiI₂, that is reactive with theworkpiece surfaces of interest. Accordingly, the silicon precursoradsorbs upon the workpiece surfaces. The first precursor pulseself-saturates the workpiece surfaces such that any excess constituentsof the first precursor pulse do not substantially react further with themolecular layer formed by this process.

The first silicon precursor pulse is preferably supplied in gaseousform. The silicon precursor gas is considered “volatile” for purposes ofthe present description if the species exhibits sufficient vaporpressure under the process conditions to transport the species to theworkpiece in sufficient concentration to saturate exposed surfaces.

In some embodiments the silicon precursor pulse is from about 0.05seconds to about 5.0 seconds, about 0.1 seconds to about 3 seconds orabout 0.2 seconds to about 1.0 second. In batch process the siliconprecursor pulses can be substantially longer as can be determined by theskilled artisan given the particular circumstances.

After sufficient time for a molecular layer to adsorb on the substratesurface, excess first precursor is then removed from the reaction space.In some embodiments the excess first precursor is purged by stopping theflow of the first precursor while continuing to flow a carrier gas orpurge gas for a sufficient time to diffuse or purge excess reactants andreactant by-products, if any, from the reaction space.

In some embodiments, the first precursor is purged for about 0.1 secondsto about 10 seconds, about 0.3 seconds to about 5 seconds or about 0.3seconds to about 1 seconds. Provision and removal of the siliconprecursor can be considered the first or silicon phase of the ALD cycle.In batch process the first precursor purge can be substantially longeras can be determined by the skilled artisan given the specificcircumstances.

A second, nitrogen precursor is pulsed into the reaction space tocontact the substrate surface. The nitrogen precursor may be providedwith the aid of a carrier gas. The nitrogen precursor may be, forexample, NH₃ or N₂H₄. The nitrogen precursor pulse is also preferablysupplied in gaseous form. The nitrogen precursor is considered“volatile” for purposes of the present description if the speciesexhibits sufficient vapor pressure under the process conditions totransport the species to the workpiece in sufficient concentration tosaturate exposed surfaces.

In some embodiments, the nitrogen precursor pulse is about 0.05 secondsto about 5.0 seconds, 0.1 seconds to about 3.0 seconds or about 0.2seconds to about 1.0 second. In batch process the nitrogen precursorpulses can be substantially longer as can be determined by the skilledartisan given the specific circumstances.

After sufficient time for a molecular layer to adsorb on the substratesurface at the available binding sites, the second, nitrogen precursoris then removed from the reaction space. In some embodiments the flow ofthe second nitrogen precursor is stopped while continuing to flow acarrier gas for a sufficient time to diffuse or purge excess reactantsand reactant by-products, if any, from the reaction space, preferablywith greater than about two reaction chamber volumes of the purge gas,more preferably with greater than about three chamber volumes. Provisionand removal of the nitrogen precursor can be considered the second ornitrogen phase of the ALD cycle.

In some embodiments, the nitrogen precursor is purged for about 0.1seconds to about 10.0 seconds, about 0.3 seconds to about 5.0 seconds orabout 0.3 seconds to about 1.0 second. In batch process the firstprecursor purge can be substantially longer as can be determined by theskilled artisan given the specific circumstances.

The flow rate and time of the nitrogen precursor pulse, as well as theremoval or purge step of the nitrogen phase, are tunable to achieve adesired composition in the silicon nitride film. Although the adsorptionof the nitrogen precursor on the substrate surface is typicallyself-limiting, due to the limited number of binding sites, pulsingparameters can be adjusted such that less than a monolayer of nitrogenis adsorbed in one or more cycles.

The two phases together represent one ALD cycle, which is repeated toform silicon nitrogen thin films of the desired thickness. While the ALDcycle is generally referred to herein as beginning with the siliconphase, it is contemplated that in other embodiments the cycle may beginwith the nitrogen phase. One of skill in the art will recognize that thefirst precursor phase generally reacts with the termination left by thelast phase in the previous cycle. In some embodiments one or moredifferent ALD cycles are provided in the deposition process.

According to some embodiments of the present disclosure, ALD reactionsmay be performed at temperatures ranging from about 25° C. to about1000° C., preferably from about 100° C. to about 800° C., morepreferably from about 200° C. to about 650° C., and most preferably fromabout 300° C. to about 500° C. In some embodiments, the optimum reactortemperature may be limited by the maximum allowed thermal budget.Therefore, the reaction temperature can be from about 300° C. to about400° C. In some applications, the maximum temperature is around about400° C., and, therefore, the process is run at that reactiontemperature.

Si Precursors

A number of suitable silicon precursors may be used in the presentlydisclosed thermal processes, such as thermal ALD processes. In someembodiments these precursors may also be used in plasma ALD processes inwhich a film with a desired quality (at least one of the desired WER,WERR, pattern loading effect or/and step coverage features describedbelow) is deposited.

According to some embodiments, some silicon precursors comprise iodineand the film deposited by using that precursor has at least one desiredproperty, for example at least one of the desired WER, WERR, patternloading effect or/and step coverage features described below.

According to some embodiments, some silicon precursors comprise bromineand the film deposited by using that precursor have at least one desiredproperty, for example at least one of the desired WER, WERR, patternloading effect or/and step coverage features described below.

At least some of the suitable precursors may have the following generalformula:

H_(2n+2−y−z−w)Si_(n)X_(y)A_(z)R_(w)  (9)

-   -   wherein, n=1-10, y=1 or more (and up to 2n+2−z−w), z=0 or more        (and up to 2n+2−y−w), w=0 or more (and up to 2n+2−y−z), X is I        or Br, A is a halogen other than X, R is an organic ligand and        can be independently selected from the group consisting of        alkoxides, alkylsilyls, alkyl, substituted alkyl, alkylamines        and unsaturated hydrocarbon; preferably n=1-5 and more        preferably n=1-3 and most preferably 1-2. Preferably R is a        C₁-C₃ alkyl ligand, such as methyl, ethyl, n-propyl or        isopropyl.

According to some embodiments, some silicon precursors comprise one ormore cyclic compounds. Such precursors may have the following generalformula:

H_(2n−y−z−w)Si_(n)X_(y)A_(z)R_(w)  (10)

-   -   wherein, n=3-10, y=1 or more (and up to 2n−z−w), z=0 or more        (and up to 2n−y−w), w=0 or more (and up to 2n−y−z), X is I or        Br, A is a halogen other than X, R is an organic ligand and can        be independently selected from the group consisting of        alkoxides, alkylsilyls, alkyl, substituted alkyl, alkylamines        and unsaturated hydrocarbon; preferably n=3-6. Preferably R is a        C₁-C₃ alkyl ligand, such as methyl, ethyl, n-propyl or        isopropyl.

According to some embodiments, some silicon precursors comprise one ormore iodosilanes. Such precursors may have the following generalformula:

H_(2n+2−y−z−w)Si_(n)I_(y)A_(z)R_(w)  (11)

-   -   wherein, n=1-10, y=1 or more (and up to 2n+2−z−w), z=0 or more        (and up to 2n+2−y−w), w=0 or more (and up to 2n+2−y−z), A is a        halogen other than I, R is an organic ligand and can be        independently selected from the group consisting of alkoxides,        alkylsilyls, alkyl, substituted alkyl, alkylamines and        unsaturated hydrocarbon; preferably n=1-5 and more preferably        n=1-3 and most preferably 1-2. Preferably R is a C1-C3 alkyl        ligand, such as methyl, ethyl, n-propyl or isopropyl.

According to some embodiments, some silicon precursors comprise one ormore cyclic iodosilanes. Such precursors may have the following generalformula:

H_(2n−y−z−w)Si_(n)I_(y)A_(z)R_(w)  (12)

-   -   wherein, n=3-10, y=1 or more (and up to 2n−z−w), z=0 or more        (and up to 2n−y−w), w=0 or more (and up to 2n−y−z), A is a        halogen other than I, R is an organic ligand and can be        independently selected from the group consisting of alkoxides,        alkylsilyls, alkyl, substituted alkyl, alkylamines and        unsaturated hydrocarbon; preferably n=3-6. Preferably R is a        C₁-C₃ alkyl ligand, such as methyl, ethyl, n-propyl or        isopropyl.

According to some embodiments, some silicon precursors comprise one ormore bromosilanes. Such precursors may have the following generalformula:

H_(2n+2−y−z−w)Si_(n)Br_(y)A_(z)R_(w)  (13)

-   -   wherein, n=1-10, y=1 or more (and up to 2n+2−z−w), z=0 or more        (and up to 2n+2−y−w), w=0 or more (and up to 2n+2−y−z), A is a        halogen other than Br, R is an organic ligand and can be        independently selected from the group consisting of alkoxides,        alkylsilyls, alkyl, substituted alkyl, alkylamines and        unsaturated hydrocarbon; preferably n=1-5 and more preferably        n=1-3 and most preferably 1-2. Preferably R is a C₁-C₃ alkyl        ligand, such as methyl, ethyl, n-propyl or isopropyl.

According to some embodiments, some silicon precursors comprise one ormore cyclic bromosilanes. Such precursors may have the following generalformula:

H_(2n−y−z−w)Si_(n)Br_(y)A_(z)R_(w)  (14)

-   -   wherein, n=3-10, y=1 or more (and up to 2n−z−w), z=0 or more        (and up to 2n−y−w), w=0 or more (and up to 2n−y−z), A is a        halogen other than Br, R is an organic ligand and can be        independently selected from the group consisting of alkoxides,        alkylsilyls, alkyl, substituted alkyl, alkylamines and        unsaturated hydrocarbon; preferably n=3-6. Preferably R is a        C₁-C₃ alkyl ligand such as methyl, ethyl, n-propyl or isopropyl.

According to some embodiments, some silicon precursors comprise one ormore iodosilanes or bromosilanes in which the iodine or bromine is notbonded to the silicon in the compound. Accordingly some suitablecompounds may have iodine/bromine substituted alkyl groups. Suchprecursors may have the following general formula:

H_(2n+2−y−z−w)Si_(n)X_(y)A_(z)R^(II) _(w)  (15)

-   -   wherein, n=1-10, y=0 or more (and up to 2n+2−z−w), z=0 or more        (and up to 2n+2−y−w), w=1 or more (and up to 2n+2−y−z), X is I        or Br, A is a halogen other than X, R^(II) is an organic ligand        containing I or Br and can be independently selected from the        group consisting of I or Br substituted alkoxides, alkylsilyls,        alkyls, alkylamines and unsaturated hydrocarbons; preferably        n=1-5 and more preferably n=1-3 and most preferably 1-2.        Preferably R^(II) is an iodine substituted C₁-C₃ alkyl ligand.

According to some embodiments, some silicon precursors comprise one ormore cyclic iodosilanes or bromosilanes. Accordingly some suitablecyclic compounds may have iodine/bromine substituted alkyl groups. Suchprecursors may have the following general formula:

H_(2n−y−z−w)Si_(n)X_(y)A_(z)R^(II) _(w)  (16)

-   -   wherein, n=3-10, y=0 or more (and up to 2n+2−z−w), z=0 or more        (and up to 2n+2−y−w), w=1 or more (and up to 2n+2−y−z), X is I        or Br, A is a halogen other than X, R^(II) is an organic ligand        containing I or Br and can be independently selected from the        group consisting of I or Br substituted alkoxides, alkylsilyls,        alkyls, alkylamines and unsaturated hydrocarbons; preferably        n=3-6. Preferably R is an iodine substituted C₁-C₃ alkyl ligand.

According to some embodiments, some suitable silicon precursors may haveat least one of the following general formulas:

H_(2n+2−y−z−w)Si_(n)X_(y)A_(z)(NR₁R₂)_(w)  (17)

-   -   wherein, n=1-10, y=1 or more (and up to 2n+2−z−w), z=0 or more        (and up to 2n+2−y−w), w=1 or more (and up to 2n+2−y−z), X is I        or Br, A is a halogen other than X, N is nitrogen and R₁ and R₂        can be independently selected from the group consisting of        hydrogen, alkyl, substituted alkyl, silyl, alkylsilyl and        unsaturated hydrocarbon; preferably n=1-5 and more preferably        n=1-3 and most preferably 1-2. Preferably R₁ and R₂ are hydrogen        or C₁-C₄ alkyl groups, such as methyl, ethyl, n-propyl,        isopropyl, t-butyl, isobutyl, sec-butyl and n-butyl. More        preferably R₁ and R₂ are hydrogen or C₁-C₃ alkyl groups, such as        methyl, ethyl, n-propyl or isopropyl. Each of the (NR₁R₂)_(w)        ligands can be independently selected from each other.

(H_(3−y−z−w)X_(y)A_(z)(NR₁R₂)_(w)Si)₃—N  (18)

-   -   wherein, y=1 or more (and up to 3−z−w), z=0 or more (and up to        3−y−w), w=1 or more (and up to 3−y−z), X is I or Br, A is a        halogen other than X, N is nitrogen and R₁ and R₂ can be        independently selected from the group consisting of hydrogen,        alkyl, substituted alkyl, silyl, alkylsilyl, and unsaturated        hydrocarbon. Preferably R₁ and R₂ are hydrogen or C₁-C₄ alkyl        groups, such as methyl, ethyl, n-propyl, isopropyl, t-butyl,        isobutyl, sec-butyl and n-butyl. More preferably R₁ and R₂ are        hydrogen or C₁-C₃ alkyl groups, such as methyl, ethyl, n-propyl        or isopropyl. Each of the (NR₁R₂)_(w) ligands can be        independently selected from each other. Each of the three        H_(3−y−z−w)X_(y)A_(z)(NR₁R₂)_(w)Si ligands can be independently        selected from each other.

In some embodiments, some suitable precursors may have at least one ofthe following more specific formulas:

H_(2n+2−y−w)Si_(n)I_(y)(NR₁R₂)_(w)  (19)

-   -   wherein, n=1-10, y=1 or more (and up to 2n+2−w), w=1 or more        (and up to 2n+2−y), N is nitrogen, and R₁ and R₂ can be        independently selected from the group consisting of hydrogen,        alkyl, substituted alkyl, silyl, alkylsilyl, and unsaturated        hydrocarbon; preferably n=1-5 and more preferably n=1-3 and most        preferably 1-2. Preferably R₁ and R₂ are hydrogen or C₁-C₄ alkyl        groups, such as methyl, ethyl, n-propyl, isopropyl, t-butyl,        isobutyl, sec-butyl and n-butyl. More preferably R₁ and R₂ are        hydrogen or C₁-C₃ alkyl groups, such as methyl, ethyl, n-propyl        or isopropyl. Each of the (NR₁R₂)_(w) ligands can be        independently selected from each other.

(H_(3−y−w)I_(y)(NR₁R₂)_(w)Si)₃—N  (20)

-   -   wherein, y=1 or more (and up to 3−w), w=1 or more (and up to        3−y), N is nitrogen and R₁ and R₂ can be independently selected        from the group consisting of hydrogen, alkyl, substituted alkyl,        silyl, alkylsilyl, and unsaturated hydrocarbon. Preferably R₁        and R₂ are hydrogen or C₁-C₄ alkyl groups, such as methyl,        ethyl, n-propyl, isopropyl, t-butyl, isobutyl, sec-butyl and        n-butyl. More preferably R₁ and R₂ are hydrogen or C₁-C₃ alkyl        groups, such as methyl, ethyl, n-propyl or isopropyl. Each of        the three H_(3−y−w)I_(y)(NR₁R₂)_(w)Si ligands can be        independently selected from each other.

According to some embodiments, some suitable silicon precursors may haveat least one of the following general formulas:

H_(2n+2−y−z−w)Si_(n)X_(y)A_(z)(NR₁R₂)_(w)  (21)

-   -   wherein, n=1-10, y=1 or more (and up to 2n+2−z−w), z=0 or more        (and up to 2n+2−y−w), w=1 or more (and up to 2n+2−y−z), X is I        or Br, A is a halogen other than −30−X, N is nitrogen, R₁ can be        independently selected from the group consisting of hydrogen,        alkyl, substituted alkyl, silyl, alkylsilyl, and unsaturated        hydrocarbon, and R₂ can be independently selected from the group        consisting of alkyl, substituted alkyl, silyl, alkylsilyl and        unsaturated hydrocarbon; preferably n=1-5 and more preferably        n=1-3 and most preferably 1-2. Preferably R₁ is hydrogen or        C₁-C₄ alkyl groups, such as methyl, ethyl, n-propyl, isopropyl,        t-butyl, isobutyl, sec-butyl, and n-butyl. More preferably R₁ is        hydrogen or C₁-C₃ alkyl groups, such as methyl, ethyl, n-propyl,        or isopropyl. Preferably R₂ is C₁-C₄ alkyl groups, such as        methyl, ethyl, n-propyl, isopropyl, t-butyl, isobutyl,        sec-butyl, and n-butyl. More preferably R₂ is C₁-C₃ alkyl        groups, such as methyl, ethyl, n-propyl, or isopropyl. Each of        the (NR₁R₂)_(w) ligands can be independently selected from each        other.

(H_(3−y−z−w)X_(y)A_(z)(NR₁R₂)_(w)Si)₃—N  (22)

-   -   wherein, y=1 or more (and up to 3−z−w), z=0 or more (and up to        3−y−w), w=1 or more (and up to 3−y−z), X is I or Br, A is a        halogen other than X, N is nitrogen, R₁ can be independently        selected from the group consisting of hydrogen, alkyl,        substituted alkyl, silyl, alkylsilyl, and unsaturated        hydrocarbon, and R₂ can be independently selected from the group        consisting of alkyl, substituted alkyl, silyl, alkylsilyl, and        unsaturated hydrocarbon; preferably n=1-5 and more preferably        n=1-3 and most preferably 1-2. Preferably R₁ is hydrogen or        C₁-C₄ alkyl groups, such as methyl, ethyl, n-propyl, isopropyl,        t-butyl, isobutyl, sec-butyl, and n-butyl. More preferably R₁ is        hydrogen or C₁-C₃ alkyl groups, such as methyl, ethyl, n-propyl,        or isopropyl. Preferably R₂ is C₁-C₄ alkyl groups, such as        methyl, ethyl, n-propyl, isopropyl, t-butyl, isobutyl,        sec-butyl, and n-butyl. More preferably R₂ is C₁-C₃ alkyl        groups, such as methyl, ethyl, n-propyl, or isopropyl. Each of        the (NR₁R₂)_(w) ligands can be independently selected from each        other.

In some embodiments, some suitable precursors may have at least one ofthe following more specific formulas:

H_(2n+2−y−w)Si_(n)I_(y)(NR₁R₂)_(w)  (23)

-   -   wherein, n=1-10, y=1 or more (and up to 2n+2−w), w=1 or more        (and up to 2n+2−y), N is nitrogen, R₁ can be independently        selected from the group consisting of hydrogen, alkyl,        substituted alkyl, silyl, alkylsilyl, and unsaturated        hydrocarbon, and R₂ can be independently selected from the group        consisting of alkyl, substituted alkyl, silyl, alkylsilyl, and        unsaturated hydrocarbon; preferably n=1-5 and more preferably        n=1-3 and most preferably 1-2. Preferably R₁ is hydrogen or        C₁-C₄ alkyl groups, such as methyl, ethyl, n-propyl, isopropyl,        t-butyl, isobutyl, sec-butyl, and n-butyl. More preferably R₁ is        hydrogen or C₁-C₃ alkyl groups, such as methyl, ethyl, n-propyl,        or isopropyl. Preferably R₂ is C₁-C₄ alkyl groups, such as        methyl, ethyl, n-propyl, isopropyl, t-butyl, isobutyl,        sec-butyl, and n-butyl. More preferably R₂ is C₁-C₃ alkyl        groups, such as methyl, ethyl, n-propyl, or isopropyl. Each of        the (NR₁R₂)_(w) ligands can be independently selected from each        other.

(H_(3−y−w)I_(y)(NR₁R₂)_(w)Si)₃—N  (24)

-   -   wherein, y=1 or more (and up to 3−w), w=1 or more (and up to        3−y), N is nitrogen, R₁ can be independently selected from the        group consisting of hydrogen, alkyl, substituted alkyl, silyl,        alkylsilyl, and unsaturated hydrocarbon, and R₂ can be        independently selected from the group consisting of alkyl,        substituted alkyl, silyl, alkylsilyl, and unsaturated        hydrocarbon; preferably n=1-5 and more preferably n=1-3 and most        preferably 1-2. Preferably R₁ is hydrogen or C₁-C₄ alkyl groups,        such as methyl, ethyl, n-propyl, isopropyl, t-butyl, isobutyl,        sec-butyl, and n-butyl. More preferably R₁ is hydrogen or C₁-C₃        alkyl groups, such as methyl, ethyl, n-propyl, or isopropyl.        Preferably R₂ is C₁-C₄ alkyl groups, such as methyl, ethyl,        n-propyl, isopropyl, t-butyl, isobutyl, sec-butyl, and n-butyl.        More preferably R₂ is C₁-C₃ alkyl groups, such as methyl, ethyl,        n-propyl, or isopropyl. Each of the (NR₁R₂)_(w) ligands can be        independently selected from each other.

According to some embodiments of a thermal ALD process, suitable siliconprecursors can include at least compounds having any one of the generalformulas (9) through (24). In general formulas (9) through (18) as wellas in general formulas (21) and (22), halides/halogens can include F,Cl, Br and I.

In some embodiments, a silicon precursor comprises one or more of thefollowing: SiI₄, HSiI₃, H₂SiI₂, H₃SiI, Si₂I₆, HSi₂I₅, H₂Si₂I₄, H₃Si₂I₃,H₄Si₂I₂, H₅Si₂I, Si₃I₈, HSi₂I₅, H₂SiI₂I₄, H₃Si₂I₃, H₄Si₂I₂, H₅Si₂I,MeSiI₃, Me₂SiI₂, Me₃SiI, MeSi₂I₅, Me₂Si₂I₄, Me₃Si₂I₃, Me₄Si₂I₂, Me₅Si₂I,HMeSiI₂, HMe₂SiI, HMeSi₂I₄, HMe₂Si₂I₃, HMe₃Si₂I₂, HMe₄Si₂I, H₂ MeSiI,H₂MeSi₂I₃, H₂Me₂Si₂I₂, H₂Me₃Si₂I, H₃MeSi₂I₂, H₃Me₂Si₂I, H₄MeSi₂I,EtSiI₃, Et₂SiI₂, Et₃SiI, EtSi₂I₅, Et₂Si₂I₄, Et₃Si₂I₃, Et₄Si₂I₂, Et₅Si₂I,HEtSiI₂, HEt₂SiI, HEtSi₂I₄, HEt₂Si₂I₃, HEt₃Si₂I₂, HEt₄Si₂I, H₂ EtSiI,H₂EtSi₂I₃, H₂Et₂Si₂I₂, H₂Et₃Si₂I, H₃EtSi₂I₂, H₃Et₂Si₂I, and H₄EtSi₂I.

In some embodiments, a silicon precursor comprises one or more of thefollowing: EtMeSiI₂, Et₂ MeSiI, EtMe₂SiI, EtMeSi₂I₄, Et₂MeSi₂I₃,EtMe₂Si₂I₃, Et₃MeSi₂I₂, Et₂Me₂Si₂I₂, EtMe₃Si₂I₂, Et₄MeSi₂I, Et₃Me₂Si₂I,Et₂Me₃Si₂I, EtMe₄Si₂I, HEtMeSiI, HEtMeSi₂I₃, HEt₂MeSi₂I₂, HEtMe₂Si₂I₂,HEt₃MeSi₂I, HEt₂Me₂Si₂I, HEtMe₃Si₂I, H₂EtMeSi₂I₂, H₂Et₂MeSi₂I,H₂EtMe₂Si₂I, H₃EtMeSi₂I.

In some embodiments, a silicon precursor comprises one or more of thefollowing: HSiI₃, H₂SiI₂, H₃SiI, H₂SiI₂I₄, H₄Si₂I₂, HSi₂I, MeSiI₃,Me₂SiI₂, Me₃SiI, Me₂Si₂I₄, Me₄Si₂I₂, HMeSiI₂, H₂Me₂Si₂I₂, EtSiI₃,Et₂SiI₂, Et₃SiI, Et₂Si₂I₄, Et₄Si₂I₂, and HEtSiI₂. In some embodiments asilicon precursor comprises two, three, four, five, six, seven, eight,nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen,seventeen, eighteen, nineteen or more compounds selected from HSiI₃,H₂SiI₂, H₃SiI, H₂SiI₂I₄, H₄Si₂I₂, HSi₂I, MeSiI₃, Me₂SiI₂, Me₃SiI,Me₂Si₂I₄, Me₄Si₂I₂, HMeSiI₂, H₂Me₂Si₂I₂, EtSiI₃, Et₂SiI₂, Et₃SiI,Et₂Si₂I₄, Et₄Si₂I₂, and HEtSiI₂, including any combinations thereof. Incertain embodiments, the silicon precursor is H₂SiI₂.

In some embodiments, a silicon precursor comprises a three iodines andone amine or alkylamine ligands bonded to silicon. In some embodimentssilicon precursor comprises one or more of the following: (SiI₃)NH₂,(SiI₃)NHMe, (SiI₃)NHEt, (SiI₃)NHiPr, (SiI₃)NHtBu, (SiI₃)NMe₂,(SiI₃)NMeEt, (SiI₃)NMeiPr, (SiI₃)NMetBu, (SiI₃)NEt₂, (SiI₃)NEtiPr,(SiI₃)NEttBu, (SiI₃)NiPr₂, (SiI₃)NiPrtBu, and (SiI₃)NtBu₂. In someembodiments, a silicon precursor comprises two, three, four, five, six,seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen ormore compounds selected from (SiI₃)NH₂, (SiI₃)NHMe, (SiI₃)NHEt,(SiI₃)NHiPr, (SiI₃)NHtBu, (SiI₃)NMe₂, (SiI₃)NMeEt, (SiI₃)NMeiPr,(SiI₃)NMetBu, (SiI₃)NEt₂, (SiI₃)NEtiPr, (SiI₃)NEttBu, (SiI₃)NiPr₂,(SiI₃)NiPrtBu, (SiI₃)NtBu₂, and combinations thereof. In someembodiments, a silicon precursor comprises two iodines and two amine oralkylamine ligands bonded to silicon. In some embodiments, siliconprecursor comprises one or more of the following: (SiI₂)(NH₂)₂,(SiI₂)(NHMe)₂, (SiI₂)(NHEt)₂, (SiI₂)(NHiPr₂, (SiI₂)(NHtBu)₂,(SiI₂)(NMe₂)₂, (SiI₂)(NMeEt)₂, (SiI₂)(NMeiPr)₂, (SiI₂)(NMetBu)₂,(SiI₂)(NEt₂)₂, (SiI₂)(NEtiPr)₂, (SiI₂)(NEttBu)₂, (SiI₂)(NiPr₂)₂,(SiI₂)(NiPrtBu)₂, and (SiI₂)(NtBu)₂. In some embodiments, a siliconprecursor comprises two, three, four, five, six, seven, eight, nine,ten, eleven, twelve, thirteen, fourteen, fifteen or more compoundsselected from (SiI₂)(NH₂)₂, (SiI₂)(NHMe)₂, (SiI₂)(NHEt)₂,(SiI₂)(NHiPr)₂, (SiI₂)(NHtBu)₂, (SiI₂)(NMe₂)₂, (SiI₂)(NMeEt)₂,(SiI₂)(NMeiPr)₂, (SiI₂)(NMetBu)₂, (SiI₂)(NEt₂)₂, (SiI₂)(NEtiPr)₂,(SiI₂)(NEttBu)₂, (SiI₂)(NiPr₂)₂, (SiI₂)(NiPrtBu)₂, (SiI₂)(NtBu)₂, andcombinations thereof.

In some embodiments, a silicon precursor comprises two iodines, onehydrogen and one amine or alkylamine ligand bonded to silicon. In someembodiments silicon precursor comprises one or more of the following:(SiI₂H)NH₂, (SiI₂H)NHMe, (SiI₂H)NHEt, (SiI₂H)NHiPr, (SiI₂H)NHtBu,(SiI₂H)NMe₂, (SiI₂H)NMeEt, (SiI₂H)NMeiPr, (SiI₂H)NMetBu, (SiI₂H)NEt₂,(SiI₂H)NEtiPr, (SiI₂H)NEttBu, (SiI₂H)NiPr₂, (SiI₂H)NiPr tBu, and(SiI₂H)NtBu₂. In some embodiments a silicon precursor comprises two,three, four, five, six, seven, eight, nine, ten, eleven, twelve,thirteen, fourteen, fifteen or more compounds selected from (SiI₂H)NH₂,(SiI₂H)NHMe, (SiI₂H)NHEt, (SiI₂H)NHiPr, (SiI₂H)NHtBu, (SiI₂H)NMe₂,(SiI₂H)NMeEt, (SiI₂H)NMeiPr, (SiI₂H)NMetBu, (SiI₂H)NEt₂, (SiI₂H)NEtiPr,(SiI₂H)NEttBu, (SiI₂H)NiPr₂, (SiI₂H)NiPrtBu, (SiI₂H)NtBu₂, andcombinations thereof.

In some embodiments, a silicon precursor comprises one iodine, onehydrogen and two amine or alkylamine ligand bonded to silicon. In someembodiments, silicon precursor comprises one or more of the following:(SiIH)(NH₂)₂, (SiIH)(NHMe)₂, (SiIH)(NHEt)₂, (SiIH)(NHiPr)₂,(SiIH)(NHtBu)₂, (SiIH)(NMe₂)₂, (SiIH)(NMeEt)₂, (SiIH)(NMeiPr)₂,(SiIH)(NMetBu)₂, (SiIH)(NEt₂)₂, (SiIH)(NEtiPr)₂, (SiIH)(NEttBu)₂,(SiIH)(NiPr₂)₂, (SiIH)(NiPrtBu)₂, and (SiIH)(NtBu)₂. In someembodiments, a silicon precursor comprises two, three, four, five, six,seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen ormore compounds selected from (SiIH)(NH₂)₂, (SiIH)(NHMe)₂, (SiIH)(NHEt)₂,(SiIH)(NHiPr)₂, (SiIH)(NHtBu)₂, (SiIH)(NMe₂)₂, (SiIH)(NMeEt)₂,(SiIH)(NMeiPr)₂, (SiIH)(NMetBu)₂, (SiIH)(NEt₂)₂, (SiIH)(NEtiPr)₂,(SiIH)(NEttBu)₂, (SiIH)(NiPr₂)₂, (SiIH)(NiPrtBu)₂, and (SiIH)(NtBu)₂,and combinations thereof.

In some embodiments, a silicon precursor comprises one iodine, twohydrogens and one amine or alkylamine ligand bonded to silicon. In someembodiments silicon precursor comprises one or more of the following:(SiIH₂)NH₂, (SiIH₂)NHMe, (SiIH₂)NHEt, (SiIH₂)NHiPr, (SiIH₂)NHtBu,(SiIH₂)NMe₂, (SiIH₂)NMeEt, (SiIH₂)NMeiPr, (SiIH₂)NMetBu, (SiIH₂)NEt₂,(SiIH₂)NEtiPr, (SiIH₂)NEttBu, (SiIH₂)NiPr₂, (SiIH₂)NiPrtBu, and(SiIH₂)NtBu₂. In some embodiments a silicon precursor comprises two,three, four, five, six, seven, eight, nine, ten, eleven, twelve,thirteen, fourteen, fifteen or more compounds selected from (SiIH₂)NH₂,(SiIH₂)NHMe, (SiIH₂)NHEt, (SiIH₂)NHiPr, (SiIH₂)NHtBu, (SiIH₂)NMe₂,(SiIH₂)NMeEt, (SiIH₂)NMeiPr, (SiIH₂)NMetBu, (SiIH₂)NEt₂, (SiIH₂)NEtiPr,(SiIH₂)NEttBu, (SiIH₂)NiPr₂, (SiIH₂)NiPrtBu, (SiIH₂)NtBu₂, andcombinations thereof.

In some embodiments, a silicon precursor comprises one iodine and threeamine or alkylamine ligands bonded to silicon. In some embodiments,silicon precursor comprises one or more of the following: (SiI)(NH₂)₃,(SiI)(NHMe)₃, (SiI)(NHEt)₃, (SiI)(NHiPr)₃, (SiI)(NHtBu)₃, (SiI)(NMe₂)₃,(SiI)(NMeEt)₃, (SiI)(NMeiPr)₃, (SiI)(NMetBu)₃, (SiI)(NEt₂)₃,(SiI)(NEtiPr)₃, (SiI)(NEttBu)₃, (SiI)(NiPr₂)₃, (SiI)(NiPrtBu)₃, and(SiI)(NtBu)₃. In some embodiments a silicon precursor comprises two,three, four, five, six, seven, eight, nine, ten, eleven, twelve,thirteen, fourteen, fifteen or more compounds selected from (SiI)(NH₂)₃,(SiI)(NHMe)₃, (SiI)(NHEt)₃, (SiI)(NHiPr)₃, (SiI)(NHtBu)₃, (SiI)(NMe₂)₃,(SiI)(NMeEt)₃, (SiI)(NMeiPr)₃, (SiI)(NMetBu)₃, (SiI)(NEt₂)₃,(SiI)(NEtiPr)₃, (SiI)(NEttBu)₃, (SiI)(NiPr₂)₃, (SiI)(NiPrtBu)₃,(SiI)(NtBu)₃, and combinations thereof.

In certain embodiments, a silicon precursor comprises two iodines,hydrogen and one amine or alkylamine ligand or two iodines and twoalkylamine ligands bonded to silicon and wherein amine or alkylamineligands are selected from amine NH₂—, methylamine MeNH—, dimethylamineMe₂N—, ethylmethylamine EtMeN—, ethylamine EtNH—, and diethylamineEt₂N—. In some embodiments silicon precursor comprises one or more ofthe following: (SiI₂H)NH₂, (SiI₂H)NHMe, (SiI₂H)NHEt, (SiI₂H)NMe₂,(SiI₂H)NMeEt, (SiI₂H)NEt₂, (SiI₂)(NH₂)₂, (SiI₂)(NHMe)₂, (SiI₂)(NHEt)₂,(SiI₂)(NMe₂)₂, (SiI₂)(NMeEt)₂, and (SiI₂)(NEt₂)₂. In some embodiments asilicon precursor comprises two, three, four, five, six, seven, eight,nine, ten, eleven, twelve or more compounds selected from (SiI₂H)NH₂,(SiI₂H)NHMe, (SiI₂H)NHEt, (SiI₂H)NMe₂, (SiI₂H)NMeEt, (SiI₂H)NEt₂,(SiI₂)(NH₂)₂, (SiI₂)(NHMe)₂, (SiI₂)(NHEt)₂, (SiI₂)(NMe₂)₂,(SiI₂)(NMeEt)₂, (SiI₂)(NEt₂)₂, and combinations thereof.

Other Types of Si-Precursors Containing I or Br

A number of suitable silicon precursors containing nitrogen, such asiodine or bromine substituted silazanes, or sulphur, may be used in thepresently disclosed thermal and plasma ALD processes. In someembodiments silicon precursors containing nitrogen, such as iodine orbromine substituted silazanes, may be used in the presently disclosedthermal and plasma ALD processes in which a film with desired quality isto be deposited, for example at least one of the desired WER, WERR,pattern loading effect or/and step coverage features described below.

At least some of the suitable iodine or bromine substituted siliconprecursors may have the following general formula:

H_(2n+2−y−z−w)Si_(n)(EH)_(n−1)X_(y)A_(z)R_(w)  (25)

-   -   wherein, y=1 or more (and up to 3−w), w=1 or more (and up to        3−y), N is nitrogen, R₁ can be independently selected from the        group consisting of hydrogen, alkyl, substituted alkyl, silyl,        alkylsilyl, and unsaturated hydrocarbon, and R₂ can be        independently selected from the group consisting of alkyl,        substituted alkyl, silyl, alkylsilyl, and unsaturated        hydrocarbon; preferably n=1-5 and more preferably n=1-3 and most        preferably 1-2. Preferably R₁ is hydrogen or C₁-C₄ alkyl groups,        such as methyl, ethyl, n-propyl, isopropyl, t-butyl, isobutyl,        sec-butyl, and n-butyl. More preferably R₁ is hydrogen or C₁-C₃        alkyl groups, such as methyl, ethyl, n-propyl, or isopropyl.        Preferably R₂ is C₁-C₄ alkyl groups, such as methyl, ethyl,        n-propyl, isopropyl, t-butyl, isobutyl, sec-butyl, and n-butyl.        More preferably R₂ is C₁-C₃ alkyl groups, such as methyl, ethyl,        n-propyl, or isopropyl. Each of the (NR₁R₂)_(w) ligands can be        independently selected from each other.

At least some of the suitable iodine or bromine substituted silazaneprecursors may have the following general formula:

H_(2n+2−y−z−w)Si_(n)(NH)_(n−1)X_(y)A_(z)R_(w)  (26)

-   -   wherein, n=2-10, y=1 or more (and up to 2n+2−z−w), z=0 or more        (and up to 2n+2−y−w), w=0 or more (and up to 2n+2−y−z), X is I        or Br, A is a halogen other than X, R is an organic ligand and        can be independently selected from the group consisting of        alkoxides, alkylsilyls, alkyl, substituted alkyl, alkylamines        and unsaturated hydrocarbon; preferably n=2-5 and more        preferably n=2-3 and most preferably 2. Preferably R is a C₁-C₃        alkyl ligand, such as methyl, ethyl, n-propyl or isopropyl.

In some embodiments, the silicon precursor comprises Si-compound, suchas heterocyclic Si compound, which comprises I or Br. Such cyclicprecursors may comprise the following substructure:

—Si-E-Si  (27)

-   -   wherein E is N or S, preferably N.

In some embodiments the silicon precursor comprises substructureaccording to formula (27) and example of this kind of compounds is forexample, iodine or bromine substituted cyclosilazanes, such iodine orbromine substituted cyclotrisilazane.

In some embodiments, the silicon precursor comprises Si-compound, suchas silylamine based compound, which comprises I or Br. Such silylaminebased Si-precursors may have the following general formula:

(H_(3−y−z−w)X_(y)A_(z)R_(w)Si)₃—N  (28)

-   -   wherein, y=1 or more (and up to 3−z−w), z=0 or more (and up to        3−y−w), w=0 or more (and up to 3−y−z), X is I or Br, A is a        halogen other than X, R is an organic ligand and can be        independently selected from the group consisting of alkoxides,        alkylsilyls, alkyl, substituted alkyl, alkylamines and        unsaturated hydrocarbon. Preferably R is a C₁-C₃ alkyl ligand,        such as methyl, ethyl, n-propyl or isopropyl. Each of the three        H_(3−y−z−w)X_(y)A_(z)R_(w)Si ligands can be independently        selected from each other.

N Precursors

According to some embodiments, the second reactant or nitrogen precursorin a thermal ALD process may be NH₃, N₂H₄, or any number of othersuitable nitrogen compounds having a N—H bond.

FIG. 4 is a flow chart generally illustrating a silicon nitride thermalALD deposition cycle that can be used to deposit a silicon nitride thinfilm in accordance with some embodiments. According to certainembodiment, a silicon nitride thin film is formed on a substrate by anALD-type process comprising multiple silicon nitride deposition cycles,each silicon nitride deposition cycle 400 comprising:

(1) contacting a substrate with a vaporized silicon precursor 410 suchthat the silicon compound adsorbs on the substrate surface;

(2) removing excess silicon precursor and any byproducts 420;

(3) contacting the substrate with a nitrogen precursor 430; and

(4) removing excess nitrogen precursor and reaction byproducts 440.

The contacting steps are repeated 450 until a thin film of a desiredthickness and composition is obtained. As mentioned above, in someembodiments the substrate may be contacted simultaneously with thesilicon compound and the nitrogen precursor, while in other embodimentsthese reactants are provided separately.

According to some embodiments, a silicon nitride thin film is depositedusing a thermal ALD process on a substrate having three-dimensionalfeatures, such as in a FinFET application. The process may comprise thefollowing steps, not necessarily performed in this order:

(1) a substrate is loaded into a reaction space;

(2) a silicon-containing precursor, such as H₂SiI₂, is introduced intothe reaction space so that the silicon-containing precursor is adsorbedto a surface of the substrate;

(3) removing excess silicon-containing precursor and reaction byproductsare removed, such as by purging;

(4) a nitrogen-containing precursor, such as NH₃ or N₂H₄, is introducedinto the reaction space to react with the silicon-containing precursoron the substrate;

(5) removing excess nitrogen-containing precursor and reactionbyproducts, such as by purging; and

(6) steps (2) through (5) may be repeated until a silicon nitride filmof a desired thickness is formed.

In some embodiments, the ALD process is performed at a temperaturebetween about 100° C. to about 800° C. or between about 200° C. andabout 600° C. or between about 300° C. to about 500° C. In someapplications, the reaction temperature is about 400° C.

SiN Film Characteristics

Silicon nitride thin films deposited according to some of theembodiments discussed herein (irrespective of whether the siliconprecursor contained bromine or iodine) may achieve impurity levels orconcentrations below about 3 at-%, preferably below about 1 at-%, morepreferably below about 0.5 at-%, and most preferably below about 0.1at-%. In some thin films, the total impurity level excluding hydrogenmay be below about 5 at-%, preferably below about 2 at-%, morepreferably below about 1 at-%, and most preferably below about 0.2 at-%.And in some thin films, hydrogen levels may be below about 30 at-%,preferably below about 20 at-%, more preferably below about 15 at-%, andmost preferably below about 10 at-%.

In some embodiments, the deposited SiN films do not comprise anappreciable amount of carbon. However, in some embodiments a SiN filmcomprising carbon is deposited. For example, in some embodiments an ALDreaction is carried out using a silicon precursor comprising carbon anda thin silicon nitride film comprising carbon is deposited. In someembodiments a SiN film comprising carbon is deposited using a precursorcomprising an alkyl group or other carbon-containing ligand. In someembodiments a silicon precursor of one of formulas (9)-(28) andcomprising an alkyl group is used in a PEALD or thermal ALD process, asdescribed above, to deposit a SiN film comprising carbon. Differentalkyl groups, such as Me or Et, or other carbon-containing ligands mayproduce different carbon concentrations in the films because ofdifferent reaction mechanisms. Thus, different precursors can beselected to produce different carbon concentration in deposited SiNfilms. In some embodiments the thin SiN film comprising carbon may beused, for example, as a low-k spacer. In some embodiments the thin filmsdo not comprise argon.

FIGS. 5A-5B show FESEM images of various silicon nitride thin filmsdeposited according to the present disclosure. After the films weredeposited, they were HF-dipped for 2 minutes. FIGS. 6A-6C show the samesilicon nitride films after the dHF drip process. Uniform etching can beseen.

According to some embodiments, the silicon nitride thin films mayexhibit step coverage and pattern loading effects of greater than about50%, preferably greater than about 80%, more preferably greater thanabout 90%, and most preferably greater than about 95%. In some casesstep coverage and pattern loading effects can be greater than about 98%and in some case about 100% (within the accuracy of the measurement toolor method). These values can be achieved in aspect ratios of more than2, preferably in aspect ratios more than 3, more preferably in aspectratios more than 5 and most preferably in aspect ratios more than 8.

As used herein, “pattern loading effect” is used in accordance with itsordinary meaning in this field. While pattern loading effects may beseen with respect to impurity content, density, electrical propertiesand etch rate, unless indicated otherwise the term pattern loadingeffect when used herein refers to the variation in film thickness in anarea of the substrate where structures are present. Thus, the patternloading effect can be given as the film thickness in the sidewall orbottom of a feature inside a three-dimensional structure relative to thefilm thickness on the sidewall or bottom of the three-dimensionalstructure/feature facing the open field. As used herein, a 100% patternloading effect (or a ratio of 1) would represent about a completelyuniform film property throughout the substrate regardless of featuresi.e. in other words there is no pattern loading effect (variance in aparticular film property, such as thickness, in features vs. openfield).

In some embodiments, silicon nitride films are deposited to athicknesses of from about 3 nm to about 50 nm, preferably from about 5nm to about 30 nm, more preferably from about 5 nm to about 20 nm. Thesethicknesses can be achieved in feature sizes (width) below about 100 nm,preferably about 50 nm, more preferably below about 30 nm, mostpreferably below about 20 nm, and in some cases below about 15 nm.According to some embodiments, a SiN film is deposited on athree-dimensional structure and the thickness at a sidewall may beslightly even more than 10 nm.

According to some embodiments silicon nitride films with various wetetch rates (WER) may be deposited. When using a blanket WER in 0.5% dHF(nm/min), silicon nitride films may have WER values of less than about5, preferably less than about 4, more preferably less than about 2, andmost preferably less than about 1. In some embodiments it could lessthan about 0.3.

The blanket WER in 0.5% dHF (nm/min) relative to the WER of thermaloxide may be less than about 3, preferably less than about 2, morepreferably less than about 1, and most preferably less than about 0.5.

And in some embodiments, the sidewall WER of the three dimensionalfeature, such as fin or trench relative to the top region WER of a threedimensional feature, such as fin or trench, may be less than about 4,preferably less than about 3, more preferably less than about 2, mostpreferably about 1.

It has been found that in using the silicon nitride thin films of thepresent disclosure, thickness differences between top and side may notbe as critical for some applications, due to the improved film qualityand etch characteristics. Nevertheless, in some embodiments, thethickness gradient along the sidewall may be very important tosubsequent applications or processes.

In some embodiments, the amount of etching of silicon nitride filmsaccording to the present disclosure may be about one or two times lessthan amount of etching observed for thermal SiO₂ (TOX) in a 0.5% HF-dipprocess (for example in a process in which about 2 to about 3 nm TOX isremoved, one or two times less SiN is removed when deposited accordingto the methods disclosed herein). The WER of preferred silicon nitridefilms may be less than that of prior art thermal oxide films.

Specific Contexts for Use of SiN Films

The methods and materials described herein can provide films withincreased quality and improved etch properties not only for traditionallateral transistor designs, with horizontal source/drain (S/D) and gatesurfaces, but can also provide improved SiN films for use onnon-horizontal (e.g., vertical) surfaces, and on complexthree-dimensional (3D) structures. In certain embodiments, SiN films aredeposited by the disclosed methods on a three-dimensional structureduring integrated circuit fabrication. The three-dimensional transistormay include, for example, double-gate field effect transistors (DG FET),and other types of multiple gate FETs, including FinFETs. For example,the silicon nitride thin films of the present disclosure may be usefulin nonplanar multiple gate transistors, such as FinFETs, where it may bedesirable to form silicide on vertical walls, in addition to the tops ofthe gate, source, and drain regions.

Another 3D structure for which the SiN deposition techniques taughtherein are particularly useful is a 3D elevated source/drain structure,as taught in U.S. Patent Publication No. 2009/0315120 A1 by Shifren etal., the disclosure of which is incorporated herein by reference in itsentirety. Shifren et al. teach elevated source/drain structures thatinclude vertical sidewalls.

Example 1

A silicon nitride thin film was deposited at 400° C. according to thepresent disclosure by a PEALD process using H₂SiI₂ as the silaneprecursor and H₂+N₂ plasma as the nitrogen precursor. This filmexhibited a combination of some of the best qualities of both ALDreaction types: the typical high quality of PEALD SiN films and theisotropic etch behavior of thermal ALD films. While these results arenot fully understood, the film properties and etch behavior werenevertheless within the specs for the high quality spacer layerapplication.

For this application, the step coverage and pattern loading effect on atrench structure with an aspect ratio of 2 should be over 95%, the wetetch rate (WER) should be less than 50% of the WER of thermally oxidizedsilicon (SiO2, TOX), and the etch rate should be about the same onhorizontal and vertical walls of the trench structure. Finally, thegrowth rate should be over 0.5 nm/min and impurity contents as low aspossible.

At 400° C. the film growth rate was 0.52 Å/cycle, and the thicknessnon-uniformity 6.2% (1−σ). The refractive index was 2.04 with anon-uniformity of 0.7% (1−σ). The growth rate per minute was not yetoptimized and was 0.13 nm/min.

The wet etch rate of a planar film was 1.13 nm/minute, which is 46.7% ofthe WER of Tox (2.43 nm/min). On a trench structure the filmconformality was from about 91.0 to about 93.1% and the pattern loadingeffect from about 95.7 to about 99.3% % as deposited (before etching).After a 2 minute dilute (0.5%) HF etch, the conformality value was fromabout 91.5 to about 94.6% and the pattern loading effect from about 97.4to about 99.5% %. The wet etch rate top region of the trench was A 4.32nm/min, B 2.98 nm/min on the trench sidewall and C 3.03 nm/min on trenchbottom. The field areas showed D 2.63 nm/min etch rate.

Without being tied to any particular theory, it is believed that itcould be beneficial that the ligand removal step of iodine or bromine iscompleted before the plasma discharge. That can avoid leftover ligandsfrom decomposing and re-entering the film as impurities, and in the caseof halides, the formation of plasma activated halides is also avoided.

The composition of a silicon nitride thin film deposited according tothe present disclosure was analyzed by HFS—RBS. The results are shown inTable 1 below. Additionally, XRR data was obtained of the same film. Thethickness of the film was determined to be about 117 nm. The massdensity was determined to be 2.63 (±0.1) g/cm³. And the surface RMSroughness was determined to be 1.76 (±0.1) nm.

TABLE 1 Film composition measured by HFS-RBS. Element Amount/atom-%Uncertainty/atom-% Si 32.7 1 N 48.9 3 H 18.3 2 Combined impurities ~0.150.15 Max. individual impurity 0.1 0.1

Example 2

Silicon nitride thin film with improved etch properties and impuritycontent (compared to example 1) were deposited in a direct plasma ALDshowerhead reactor by PEALD processes according to the presentdisclosure. Susceptor temperatures of 200° C. and 400° C. were used.H2SiI2 was used as the silicon precursor and H₂+N₂ plasma was used asthe nitrogen precursor. Plasma power was from about 200 W to about 220 Wand the gap between the showerhead plate and susceptor (i.e. the spacewhere plasma is generated) was 10 mm. The plasma did not contain Ar.Nitrogen was used as a carrier gas and was flowed throughout thedeposition process. H₂SiI₂ consumption was about 9.0 mg/cycle.

At 400° C. the films growth rate was 0.7 Å/cycle and the deposited filmswere conformal. The refractive indexes were 1.92-1.93. The wet etchrates (WER) of planar films in 100:1 dHF were from about 20 to 30% ofthe WER of thermal oxide (SiO₂). On a trench structure the film wet etchrate ratio of trench sidewall to trench top varied from about 0.8 toabout 1.0.

The impurity content of silicon nitride thin films deposited at 200° C.were analyzed by TXRF. Films contained 8.43×10¹² iodine atoms per cm²,which is slightly less than the impurity content (1.418×10¹³ iodineatoms per cm²) of films deposited using plasma containing Ar in additionto H₂+N₂ plasma. In addition, films deposited at 400° C. usingAr-containing plasma had Ar as an impurity (8.067×10¹³ argon atoms percm²) as evidenced by TXRF analysis. Without being tied to any particulartheory, it is believed that argon could be trapped inside the film andthat by using plasma that does not contain argon this can be avoided.

It will be understood by those of skill in the art that numerous andvarious modifications can be made without departing from the spirit ofthe present invention. The described features, structures,characteristics and precursors can be combined in any suitable manner.Therefore, it should be clearly understood that the forms of the presentinvention are illustrative only and are not intended to limit the scopeof the present invention. All modifications and changes are intended tofall within the scope of the invention, as defined by the appendedclaims.

What is claimed is:
 1. A plasma enhanced atomic layer deposition (PEALD)process for depositing a silicon nitride thin film on a substrate in areaction space comprising: contacting the substrate with a vapor phasesilicon reactant having the formula H_(2n+2−y−z)Si_(n)X_(y)A_(z), whereX is I or Br, A is a halogen other than X and n=1, y=1 and z=0; andcontacting the substrate with reactive species generated by a plasmafrom a nitrogen precursor; wherein a ratio of an etch rate of thesilicon nitride thin film in 0.5% aqueous HF deposited on a sidewall ofa three-dimensional feature to an etch rate of the silicon nitride filmin 0.5% aqueous HF deposited on a top surface of the three-dimensionalfeature is less than
 2. 2. The process of claim 1, wherein thecontacting steps comprise a deposition cycle and the process comprisestwo or more deposition cycles.
 3. The process of claim 2, furthercomprising repeating the deposition cycle until a silicon nitride thinfilm of a desired thickness has been formed.
 4. The process of claim 2,wherein the deposition cycle further comprises removing excess siliconreactant and reaction byproducts, if any, after contacting the substratewith the silicon reactant and removing excess reactive species andreaction byproducts, if any, after contacting the substrate withreactive species.
 5. The process of claim 1, wherein the reactivespecies comprises hydrogen, hydrogen atoms, hydrogen plasma, hydrogenradicals, N*, NH* or NH₂* radicals.
 6. The process of claim 1, whereinthe nitrogen precursor comprises a gas selected from the groupconsisting of N₂ and an N₂/H₂ mixture.
 7. The process of claim 1,wherein the silicon reactant comprises H₃SiI.
 8. The process of claim 1,wherein the silicon reactant comprises H₃SBr.
 9. The process of claim 1,wherein an etch rate of the silicon nitride thin film is less than 4nm/min in 0.5% aqueous HF.
 10. The process of claim 1, wherein thesilicon nitride thin film exhibits a step coverage and pattern loadingeffect of at least 80%
 11. The process of claim 1, wherein the ratio isabout
 1. 12. A plasma enhanced atomic layer deposition (PEALD) processfor forming a silicon nitride thin film on a substrate in a reactionspace comprising a plurality of deposition cycles, each deposition cyclecomprising: alternately and sequentially contacting the substrate with avapor phase silicon reactant and reactive species comprising nitrogen;wherein the vapor phase silicon reactant has the formulaH_(2n+2−y−z)Si_(n)X_(y)A_(z), where X is I or Br, A is a halogen otherthan X and n=1, y=1 and z=0, and wherein a ratio of an etch rate of thesilicon nitride thin film in 0.5% aqueous HF deposited on a verticalsurface of a three-dimensional feature to an etch rate of the siliconnitride film in 0.5% aqueous HF deposited on a horizontal surface of thethree-dimensional feature is less than
 2. 13. The process of claim 12,wherein the reactive species are generated by a plasma from a nitrogenreactant gas.
 14. The process of claim 13, wherein the nitrogen reactantgas comprises a gas selected from N₂ and an N₂/H₂ mixture.
 15. Theprocess of 13, wherein the nitrogen reactant gas comprises N₂ and H₂gases.
 16. The process of claim 12, wherein the reactive species aregenerated directly above the substrate.
 17. The process of claim 12,wherein the reactive species are generated in a remote plasma generator.18. The process of claim 12, wherein the silicon reactant comprisesH₃SiI.
 19. The process of claim 12, wherein the silicon reactantcomprises H₃SiBr.
 20. The process of claim 12, wherein the siliconnitride thin film is deposited during the formation a FinFET.